Disazo pigments and method of producing



Patented Nov. 30, 1943 UNITED l STATES PATENT OFFICE,

DISAZO PIGM'ENTS ANDIHETHOD OF 7 PRODUCING Williain B. Reynolds,Elmhurst, Long Island, N. Y., assignorto Intel-chemical Corporation, NewYork,'N. Y., a corporation of Ohio No'Drawing. Application June 12,1940,

Serial N0. 340,046

- ,7 Claims. (Cl. 260 148) This invention relates to disazo pigments,and Example 1 g has particular reference to new plgmeints 246 parts ofdianisidine are slurried with 3000 acterized by cleanliness of tonecombined with parts of Water and 138 parts of sodium nitrite fastness tolight and resistance to bleeding in The Slurry is iced to C andtetrazotized organic solvents. Specifically, this invention 5theaddition of 250 parts'of ION hydrochloric relates to.the coppercomplexes i l from acid. The tetrazo thus prepared is run into a the(louphngs beta naphthmp l Wlth cold coupling solution prepared bydissolving 370 certain tetrazotized primary aromatic d1amines. parts ofbeta hydroxy naphthoic acid in 5000 Thgre has been .corlside-rabl-e.dqnanvdbpartlcu' parts of water with 500 parts of soda ash. WhenIa'flym the field of plgment prmtmg on textlles 1O coupling is completethe charge is heated with for pigments which would combine the featuresvSteam to 90 C and coppered by the gradual of brilliance of tone,fastness to light, and resistadd1t1on of 540 parts of blue vitrioldlssolved 1n ance to solvents such as acetone, while showing 1500 partsof hot water The charge is held at extremely good resistance to waterand dilute 90400, C for 1A2 hour l filtered andwashed soap solutions. Inparticular, acceptable browns 5 and violets have been difiicult toobtain unless 2?? g 225 Obtamed 1S Very clean insoluble vat dyestuffsare used. ms gray plg e I have discovered certain azo pigments whichEflla'mple 2 combine cleanliness of color with light fastness, 252 partsof dichlor benzidine substituted f wash-resistance and insolubility inorganic s01- the, diavnisidine gives a reddish gray pigment vents' Thesepl'gmenFs compnse the copperefi 184 parts of benzidine yields a blueviolet, while complexes of the couplings of beta oxy naphthorc tolidmegives a bright blue gray acid with tetrazotized primary aromaticdiamines The typi c M precautionary measures useful in of generalformula: diazotization reactions should be observed, these NH2-R X 1 y 22,,, varying of course with the particular amine. In

coupling, I prefer to operate with the beta oxy where R and R arebenzene 0r naphthalene naphthoic acid partially out of solution, as Ifind nuclei, X1 and X are substituents of the r up that improved resultsare obtained in more connsist n of hyd en alkyl, a yl, aralky akcentrated coupling solutions. oxy, halogen and nitro, n and n arenumbers The copper probably couples by forming a from 1 t0 3, and Y is abond, y Carbonyl complex between the phenolic hydroxyl and the ycarboxyl group. I find that about 10, to 15% e colors Produced y inShade, being excess of copper is desirable over that necessary browns,dull blues and violets of good cleanliness. t produce the theoreticalequi-molar complex They may e represented by the general formula! 3?with the beta-oxy naphthoic acid (i. e. two mols of copper per mol ofdyestufi). The coppering I N:N RIXI" Y R2XZ"T NZN can take place inneutral or alkaline solutions I (pH 7.0 or higher), the copper may bepresent -OH HO- Cu as a simple salt, or as a complex such as the copperammonium complex. In general, rather I COOH H000 elevated temperatures(GO-100 C.) are necessary to insure complete ooppering.

where R and R are benzene or naphthalene Obviously, many changes can bemade in the nuclei, X and X are substituents of the group specificexamples without departing from the Consisting o hydrogen alkyl, y yscope of the invention, which is defined in the oxy, halogen and nitro,n and n are numbers 1aims from 1 to 3, and Y is a bond, oxygen, carbonylI 1 or alkyl. 1, As new pigment dyestuffs, co-mpoundsof the Typicalamines which can be used include genera] formula;

benzidine, tolidine, dianisidine, dichlor benzidine, N=N R1X! tetrachlor benzidine, diamino diphenyl ether,

diamino benzo phenone and diamino diphenyl methane. C11

Typical examples of my invention are the following: 5

OH COOH V in the form f finely divided water-insoluble pig'- mentpowders.

3. As new pigment dyestufis, compounds of the,

following formula:

COOH OH OCH: OCH: OH COOH in the form of finely divided water-insolublepigment powders.

4. As new pigment dyestuffs, compounds of the following formula: coon on01 01 on coon in the form of finely divided water-insoluble pig-' mentpowders.

5. The method of making a pigment dyestuff, which comprisestetrazotizing a diamine of the formula:

where X and X are substituents of the group consisting of hydrogen,alkyl, alkoxy, halogen and nitro, n and n" are numbers from 1 to 3, Y isa connecting member of the group consisting of a bond, oxygen, carbonyland alkyl, and R and R are nuclei of the group consisting of benzene andnaphthalene, coupling the tetrazo compound with beta hydroxy naphthoicacid, and coppering in substance the azo compound so produced.

6. The method of making a pigment dyestufi, which comprisestetrazotizing a diamine of the formula:

where X and X are substituents of the group consisting of hydrogen,alkyl, alkoxy, halogen and-nitro, n and n are numbers from 1 to 3, Y isa connecting member of the group consisting of a bond, oxygen, carbonyland alkyl, and R and R are nuclei of the group consisting of benzene andnaphthalene, coupling the tetrazo compound with-beta hydroxynaphthoicacid, and coppering in substance theazo compound soproducedbyitreatment with a copper compound at a pH of at least 7 .0.

7. The-method of making a pigment dyestufi, which comprisestetrazotizing a diamine of th formula: V f

where X and X. are substituents of th group consisting ofhydrogen,a1kyd, alkoxy, halogen andnitro, n and n are numbers from iv tov3, Y is a connecting member of the group'consis t ing of a bond,oxygen, carbonyl and alkyL'and R and R are nuclei of the groupconsisting of benzene and naphthalene, coupling the tetraz o compoundwith beta hydroxy naphtholc acid, and coppering in substance the azocompound so produced by treatment with a copper compound at a pH of atleast 7.0 at a temperature of at least C. I 7,

WILLIAM B. REYNOLDS.

